JP2009507246A - Charge conducting media - Google Patents

Abstract

An electrochromic assembly (32) is disclosed. The assembly is a first and second electrode (22, 24) at least one of which is transparent; a porous membrane (10) defining a plurality of pores having a first refractive index. And a porous membrane (10) disposed between the electrodes (22, 24); an electrolyte filling the pores, the second substantially matching the first refractive index An electrolyte having an index of refraction and the electrolyte and membrane together forming a substantially transparent electrolyte layer; and at least one electro covering at least a portion of the first electrode (22) A chromic layer (18). The membrane 10 is flexible and the spacing between the electrodes (22, 24) is maintained substantially constant by the membrane (10). The membrane is sealed with a sealant (42).
[Selection] Figure 5c

Description

  The present invention relates to an electrochromic assembly, and in particular to an electrochromic assembly having the ability to change the amount of transmitted or reflected light.

  Modern vehicles include an indoor rear view mirror that is placed in a position where, during use, the driver can see other vehicles traveling behind his vehicle. During night driving conditions, glare caused by the reflection of subsequent vehicle headlights by these rear view mirrors is a problem for the driver. It is necessary to suppress this glare so that the driver can continuously see the back of the vehicle.

  A known solution for nighttime headlight glare comprises an indoor rear view mirror that can be manually operated between a daytime reflection position and a nighttime reflection position. These mirrors use a first surface reflection and a second surface reflection from a prism having a reflective coating on one surface.

  Window panes are widely used in buildings and vehicles and typically allow light and other radiation to enter a sealed space such as a room or vehicle interior. The intensity of light, especially the intensity of sunlight, is often a problem when the light is very bright, or when the radiation heats the interior or fades objects inside the room or inside the vehicle compartment. In some cases, it is necessary to reduce the intensity of light transmitted to a room or a vehicle interior and to allow a slight amount of light to enter. Window glare can be suppressed by tinting the window, but tinting permanently reduces the light transmittance of the window.

  Other panes can be used inside the building or vehicle to partition the part. For example, a driver of a vehicle and passengers behind it can be separated by a window, or a private office area and a public space can be separated by a window. Also, in some cases, it is necessary to reduce the transparency of such window glass in order to increase the level of privacy in a certain area. If transparency is reversible, tinting the window permanently reduces transparency, so tinting the window is still not a satisfactory solution.

  It is known that electrochromics can be used to reduce the intensity of light reflected from the vehicle rear view mirror, or alternatively to reduce the transmittance of light transmitted through the window glass. Electrochrome is an inorganic or organic material whose absorption characteristics change due to charge transfer or electron transfer when a voltage potential is applied. This absorption change usually causes a change in the color or transparency of electrochrome. An electrochromic assembly typically has two electrodes and electrochrome arranged to be affected by the voltage potential applied across these electrodes, and to the electrochrome by the voltage potential applied across the electrodes. The charge transfer is promoted. By appropriately changing the voltage potential, the transmission characteristics of electrochrome can be changed. Obviously, this effect can be used to advantage in the manufacture of windows and mirrors.

  A problem with known electrochromic assemblies using conventional liquid electrolytes is that the lifetime of the assembly is relatively short compared to the lifetime of the vehicle mirror or window glass. This short lifetime of electrochromic assemblies is attributed to electrochemical degradation due to over-oxidation or over-reduction of electrochrome and / or electrodes that degrade the assembly. Replacing the electrochromic assembly is costly and cumbersome for the user.

  Another problem with known electrochromic assemblies containing liquid electrolytes is that liquids can leak out of the assembly and harm the surrounding environment. This leakage can occur during normal operation or it can occur following an impact, for example during an accident. Another drawback of assemblies containing a liquid electrolyte is that the profile (ie thickness) of the assembly containing the liquid because a separator is required to separate the two electrodes so that they do not contact each other. It is difficult to reduce the thickness. Usually, the separator is a gasket around the boundary of the assembly, but it is difficult to maintain a uniform gap between the electrodes and the gap between the electrodes due to external or internal stress. Can change, which can cause the electric field to collapse and non-uniform performance. This is evident in LCD displays where the display changes color over a wide range due to externally applied pressure. This is particularly difficult when trying to build a physically large and curved electrochromic assembly in a single plane or across two planes. This additional complexity further increases costs and makes manufacturability difficult.

  Another problem with known electrochromic assemblies is that the materials that make up the electrochromic assemblies are often harmful to health and the environment. For example, viologens are widely used as electrochromics, but viologens are toxic when in contact with skin or swallowed. Viologens also irritate the respiratory system and skin, are toxic to aquatic organisms, and can adversely affect the aqueous environment for extended periods of time.

  One alternative to liquid electrolytes is a solid electrolyte. Electrochromic assemblies with solid electrolytes typically have a much longer life than assemblies containing only liquid electrolytes. The disadvantage of solid electrolytes is that the electrochromic layer and the solid electrolyte usually have a rigid structure that must continually expand and contract to allow ions to enter and exit the electrochromic layer. Eventually, mechanical strain develops to the interface between the electrochromic layer and the solid electrolyte, and the entire electrochromic assembly is deteriorated. In particular, such assemblies exhibit hazing or crazing due to light scattered by the cracks, and the resulting disturbing ion flow reduces changes in the color or transparency of the assembly.

  Furthermore, known electrochromic assemblies can be difficult and / or expensive to assemble during manufacture, and are therefore disadvantageous for effective and cost-effective manufacture.

  Accordingly, there is a need for a charge conducting medium suitable for use in electrochromic assemblies, and in particular, a charge conducting medium in which the color, transparency, or reflectivity of the associated electrochrome changes rapidly.

It is an object of the present invention to provide an improved electrochromic assembly that solves or at least alleviates some of the problems with the prior art described above.
Hereinafter, although the outline | summary is demonstrated in relation to the light control mirror for using for a motor vehicle, the following description does not restrict | limit this invention at all. The present invention can be applied to other systems where the reflectance or transmittance of light or other radiation needs to be reduced, for example, but not limited to, electrochromic glazing. Applicable to eye related applications, visual displays or clothing.

According to a first aspect of the invention,
First and second flexible electrodes, at least one of which is transparent;
A porous flexible membrane having a plurality of pores, the porous flexible membrane having a first refractive index and disposed between the electrodes; and the first or At least one electrochromic layer covering at least a portion of any of the second electrodes;
An electrochromic subassembly comprising:
The subassembly is flexible and transmits an electrolyte having a second refractive index that is substantially matched to the first refractive index, and the electrolyte and subassembly together are substantially transparent electrochromic An electrochromic subassembly is provided that can form an assembly.

The subassembly is preferably flexible with a diameter of 400 millimeters. More preferably, the subassembly has a flexibility of 100 millimeters in diameter.
The electrolyte can be selected from the group comprising an ionic liquid, an essentially non-liquid salt, a solvent, a polymer having an anionic functional group or a cationic functional group. The electrolyte is preferably an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.
In this electrochromic subassembly (claim 2), the assembly comprises a first electrochromic layer on the first side of the membrane and a second electrochromic layer on the second side of the membrane. be able to.
The first electrochromic layer preferably has an absorption spectrum that is complementary to the absorption spectrum of the second electrochromic layer.

  The first electrochromic layer and the second electrochromic layer have a combined (matched) that is maximum over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. E) may have an absorption spectrum. The first electrochromic layer and the second electrochromic layer are combined (combined) that are minimal over the visible spectrum when a reverse potential is applied between the first electrochromic layer and the second electrochromic layer. ) It preferably has an absorption spectrum.

At least one electrochromic layer can contain an essentially conductive polymer.
Intrinsically conductive polymers include polypyrrole and its derivatives, polythiophene and its derivatives, polyaniline and its derivatives, polycarbazole and its derivatives, polyphenylene sulfide and its derivatives, polyparaphenylene and its derivatives or polyindole and its derivatives. It preferably contains one or more monomer units or oligomers selected from the group comprising. More preferably, the first electrochromic layer contains poly-3,4-alkylenedioxy-thiophene, and the second electrochromic layer is polypyrrole.
Preferably, the at least one electrochromic layer further contains a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives and antifoaming agents.

Also, the at least one electrochromic layer can further contain a conductive additive that substantially improves the conductivity of the electrochromic layer. The conductive additive preferably contains indium-tin oxide (ITO) particles.
The electrode can be selected from the group comprising indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO). Preferably, at least one of the electrodes has a plurality of pores, the pores of the electrode being capable of transporting ions through them through them.

The porous flexible membrane can contain a polymer. The porous flexible membrane preferably contains polyvinylidene difluoride (PVDF). More preferably, the membrane is substantially opaque in the visible spectrum.
The pores of the flexible membrane can have tortuous passages through the membrane that allow electrolyte to pass through the membrane. The pore size of the porous membrane is preferably between 50 nm and 100 μm. More preferably, the pore size of the porous membrane is between 0.1 μm and 5 μm.

According to a second aspect of the invention,
First and second electrodes, at least one of which is transparent;
A porous membrane having a plurality of pores, the porous membrane having a first refractive index and disposed between the electrodes;
An electrolyte filling the pores, wherein the electrolyte has a second refractive index that is substantially compatible with the first refractive index, and the electrolyte and the membrane together are substantially transparent An electrolyte forming a layer; and at least one electrochromic layer covering at least a portion of either the first or second electrode;
An electrochromic assembly is provided.

  Preferably, the membrane is flexible and the spacing between the first electrode and the second electrode is maintained substantially constant by the membrane. The assembly formed using this membrane is preferably flexible.

The electrolyte can be selected from the group comprising an ionic liquid, an essentially non-liquid salt, a solvent, a polymer having an anionic functional group or a cationic functional group. The electrolyte is preferably an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.
The assembly can comprise a first electrochromic layer on the first side of the membrane and a second electrochromic layer on the second side of the membrane. The first electrochromic layer preferably has an absorption spectrum that is complementary to the absorption spectrum of the second electrochromic layer.
The first electrochromic layer and the second electrochromic layer are combined (combined) that are maximal over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. It can have an absorption spectrum. The first electrochromic layer and the second electrochromic layer are combined (combined) that are minimal over the visible spectrum when a reverse potential is applied between the first electrochromic layer and the second electrochromic layer. ) It preferably has an absorption spectrum.

At least one electrochromic layer can contain an essentially conductive polymer.
Intrinsically conductive polymers include polypyrrole and its derivatives, polythiophene and its derivatives, polyaniline and its derivatives, polycarbazole and its derivatives, polyphenylene sulfide and its derivatives, polyparaphenylene and its derivatives or polyindole and its derivatives. It preferably contains one or more monomer units or oligomers selected from the group comprising. More preferably, the first electrochromic layer contains poly-3,4-alkylenedioxy-thiophene, and the second electrochromic layer is polypyrrole.

The at least one electrochromic layer may further contain performance additives selected from the group comprising preservative additives, wetting agents, rheological additives and antifoaming agents.
The at least one electrochromic layer can further contain a conductive additive that substantially improves the conductivity of the electrochromic layer. The conductive additive preferably contains indium tin oxide (ITO) particles.

The electrode can be selected from the group comprising indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO). Preferably, at least one of the electrodes has a plurality of pores, the pores of the electrode being capable of transporting ions through them through them.
The porous flexible membrane can contain a polymer. The porous flexible membrane preferably contains polyvinylidene difluoride (PVDF). More preferably, the membrane is substantially opaque in the visible spectrum.
The pores of the flexible membrane preferably have tortuous passages through the membrane that allow electrolyte to pass through the membrane. The pore size of the porous membrane can be between 50 nm and 100 μm. More preferably, the pore size of the porous membrane is between 0.1 μm and 5 μm.

The electrochromic assembly preferably further comprises a reflective surface so that the assembly forms an electrically dimmable mirror.
The reflective surface is preferably formed by either the first or second electrode.

The assembly can further comprise means for changing the voltage potential between the electrodes. The change in potential induces a change in the light transmittance of the assembly.
According to a third aspect of the invention,
A preformed porous membrane having a first refractive index having a plurality of pores;
An ionic liquid filling the pores, wherein the ionic liquid has a second refractive index substantially matching the first refractive index, the ionic liquid and the membrane together An ionic liquid forming a substantially transparent layer;
At least one essentially conductive polymer electrochromic layer covering at least a portion of the membrane;
A charge conducting medium comprising:
A charge conducting medium is provided in which the membrane pores are sized so that substantially uninhibited ions flow through the membrane so that ions of the ionic liquid can interact with the electrochromic layer. The
The charge conducting medium is further
A first electrode; and a second electrode spaced from the first electrode, wherein the charge conducting medium and the electrochromic layer are disposed between the electrodes;
Can be provided.
The charge conducting medium is preferably flexible with a diameter of 400 millimeters. More preferably, the charge conducting medium has a flexibility of 100 millimeters in diameter.
The electrolyte can be selected from the group comprising an ionic liquid, an essentially non-liquid salt, a solvent, a polymer having an anionic functional group or a cationic functional group. The electrolyte is preferably an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.
The assembly can comprise a first electrochromic layer on the first side of the membrane and a second electrochromic layer on the second side of the membrane.
The first electrochromic layer preferably has an absorption spectrum that is complementary to the absorption spectrum of the second electrochromic layer.
The first electrochromic layer and the second electrochromic layer are combined (combined) that are maximal over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. It can have an absorption spectrum. The first electrochromic layer and the second electrochromic layer are combined (combined) that are minimal over the visible spectrum when a reverse potential is applied between the first electrochromic layer and the second electrochromic layer. ) It preferably has an absorption spectrum.
At least one electrochromic layer can contain an essentially conductive polymer.
Intrinsically conductive polymers include polypyrrole and its derivatives, polythiophene and its derivatives, polyaniline and its derivatives, polycarbazole and its derivatives, polyphenylene sulfide and its derivatives, polyparaphenylene and its derivatives or polyindole and its derivatives. It preferably contains one or more monomer units or oligomers selected from the group comprising. More preferably, the first electrochromic layer contains poly-3,4-alkylenedioxy-thiophene, and the second electrochromic layer is polypyrrole.
The at least one electrochromic layer can further contain performance additives selected from the group comprising preservative additives, wetting agents, rheology additives and antifoaming agents.
The at least one electrochromic layer can further contain a conductive additive that substantially improves the conductivity of the electrochromic layer. The conductive additive preferably contains indium tin oxide (ITO) particles.
The electrode can be selected from the group comprising indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO). Preferably, at least one of the electrodes has a plurality of pores, the pores of the electrode being capable of transporting ions through them through them.
The porous flexible membrane preferably contains a polymer. More preferably, the porous flexible membrane contains polyvinylidene difluoride (PVDF).
The membrane may be substantially opaque in the visible spectrum. The pores of the flexible membrane preferably have tortuous passages through the membrane that allow electrolyte to pass through the membrane. The pore size of the porous membrane can be between 50 nm and 100 μm. More preferably, the pore size of the porous membrane is between 0.1 μm and 5 μm.
According to a fourth aspect of the invention,
Providing first and second transparent sheets each having a conductive electrochromic layer forming an electrode;
Providing a preformed porous flexible membrane having a first refractive index;
Filling the membrane with an electrolyte having a second refractive index substantially matching the first refractive index;
Sealing the membrane and electrolyte between the first sheet and the second sheet;
Forming a substantially transparent electrochromic assembly having a light transmittance that varies with the voltage applied between the electrodes by the steps described above;
An electrochromic assembly manufacturing method is provided.
The porous flexible membrane preferably contains a polymer. More preferably, the porous flexible membrane contains polyvinylidene difluoride (PVDF).
The membrane can be selected to have a pore size between 50 nm and 100 μm. More preferably, the membrane is selected to have a pore size between 0.1 μm and 5 μm.
The electrolyte can be selected from the group comprising an ionic liquid, an essentially non-liquid salt, a solvent, a polymer having an anionic functional group or a cationic functional group. The electrolyte is preferably an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.
The method further includes the step of adding a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives and antifoaming agents to at least one of the plurality of conductive electrochromic layers. Can do.

According to a fifth aspect of the present invention,
Providing a preformed porous flexible membrane having a first refractive index having a plurality of pores;
Adding a first conductive material to the first side of the membrane to form a first electrode;
Adding a second conductive material to the second side of the membrane to form a second electrode;
Adding a first electrochromic material to the first side of the membrane;
Filling the membrane with an electrolyte having a second refractive index substantially matching the first refractive index;
Forming a substantially transparent electrochromic assembly having a light transmittance that varies with the voltage applied between the electrodes by the steps described above;
A method of manufacturing a flexible electrochromic assembly is provided.
Preferably, the method further includes the step of adding a second electrochromic material to the second side of the membrane.

The step of adding the first conductive material and the step of adding the first electrochromic material may be a single step that forms the first single layer, and the first conductive material and the first The electrochromic materials may be the same material or a mixture of materials.
The formed assembly is preferably flexible with a diameter of 400 millimeters. More preferably, the assembly is flexible with a diameter of 100 millimeters.
The method further includes the step of adding a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives and antifoaming agents to at least one of the plurality of conductive electrochromic layers. Can do.

  The porous flexible membrane preferably contains a polymer. More preferably, the porous flexible membrane contains polyvinylidene difluoride (PVDF). The membrane can be selected to have a pore size between 50 nm and 100 μm. More preferably, the pore size is between 0.1 μm and 5 μm.

Unless the context requires otherwise, throughout this specification and claims, the phrases “comprising” and “including”, and variations thereof such as “comprising” and “including” It should be understood that the phrase implies that the referenced full or complete group is included, but is not exclusive of any other complete or complete group.
All prior art references in this specification either acknowledge that such prior art forms part of general common knowledge, or suggest in some way that this is the case. It's not what you have. Also, prior art references herein should not be construed as such.

Specific embodiments of the present invention shown in the accompanying drawings will now be described in some detail with reference to the drawings. These embodiments are for illustrative purposes and do not limit the scope of the present invention. Although not shown in the accompanying drawings, proposals and descriptions of other embodiments may be included within the scope of the present invention, or may not be described herein, In some cases, features of the present invention are shown.
The accompanying drawings illustrate example embodiments of the invention.

  Referring to FIG. 1 a, membrane 10 is a preformed porous flexible polymeric material having a plurality of pores 12. Since the pores of the membrane 10 scatter light, the membrane is therefore opaque (optically opaque) in the visible region of the electromagnetic spectrum. The arrows in FIG. 1a indicate the direction of light incident on the membrane. Being opaque means that up to about 93% of the light incident on the membrane is reflected and about 7% of the light is transmitted. The structure of the membrane 10 is described as a tortuous structure and is effectively a loose open cell sponge type.

  In this embodiment, the membrane 10 is made of a harmless flexible free-standing polymer sheet or polymer polyvinylidene difluoride (PVDF) in the form of a membrane. The diameter of the pores of the membrane 10 is between 50 nanometers (nm) and 100 micrometers (μm). In a preferred embodiment, the spectroscopically accurately measured average pore diameter range is between about 0.1 and 5 micrometers (μm). FIG. 2a shows a close-up view of the PVDF membrane 10 used in this structure.

  The membrane 10 is flexible and self-supporting and includes pores or passages that can be filled with liquid. It will be appreciated that any membrane having the required mechanical properties can be used, and that the structure of the membrane need not be a tortuous structure. Also, the membrane 10 can support the electrochromic layer and / or electrode on its surface without significant loss of porosity (described below).

  In FIG. 1 b, the membrane 10 comprises an electrolyte 14 filled in the pores 12. The electrolyte can pass through the membrane through a tortuous path formed by the pores. However, the electrolyte is retained within the membrane polymer substrate by capillary forces. The electrolyte is preferably an ionic liquid, but the electrolyte can be any combination of ionic liquids, ionic liquids and essentially non-liquid salts such as NaCl, or ionic liquids and solvents, or mixtures thereof. It will be understood that a combination of these may be used. The electrolyte may be a polymer having an anionic functional group or a cationic functional group. Alternatively, the electrolyte may be a salt with a supporting solvent.

  In a preferred embodiment, the ionic liquid is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide. Other suitable ionic liquids include, for example, n-butyl-n-methylpyrrolidinium bistrifluoromethanesulfonimide. Once filled, the ionic liquid 14 and the membrane 10 form an electrolytic layer 16. About 80% of the mass of the layer is ionic liquid 14. The electrolytic layer 16 is a non-poisonous flexible solid system that functions as a charge conducting medium. A membrane containing a liquid electrolyte will damage surrounding inclusions.

  The ionic liquid 14 is selected (or adjusted) such that when the ionic liquid is added to the membrane 10, the electrolytic layer or charge conducting medium 16 formed is substantially transparent. The optical opacity and optical transparency of the electrochromic assembly shown in FIGS. 1a and 1b are indicated using arrows indicating reflected or transmitted light. In FIG. 1a, light is reflected from the opaque surface of the membrane 10 (as described above). In FIG. 1 b, light has passed through the electrolytic layer 16.

  The ionic liquid 14 is advantageously used without the need for a supporting solvent, and does not easily evaporate even if it is exposed to the atmosphere for a long time (the concentration of an electrolyte that requires a supporting solvent changes as the solvent evaporates). To do). Ionic liquids have high conductivity, have a large electrochemical window (stable over a potential range of 4 to 6 volts), and have fast charge carrier mobility during redox. Furthermore, since it is non-volatile and non-flammable, it is an ideal electrolyte.

  The optical transparency of the electrolytic layer 16 is achieved by substantially matching the refractive index of the ionic liquid 14 and the refractive index of the membrane 10. When the pores 12 of the membrane 10 are filled with the ionic liquid 14, air is expelled, thereby forming a substantially uniform refractive index throughout the membrane. To ensure a reasonably good refractive index match, an ionic liquid can be selected that meets the required refractive index, or the refractive index can be changed by adding additives such as zirconium oxide particles. Further, the refractive index of the ionic liquid can be changed by changing the electrolyte salt, for example.

  The transmittance of light passing through the electrolytic layer 16 is actually improved (increased) compared to the transmittance of light passing through the air. This electrolytic layer or charge conducting medium is a medium with specular quality and provides a non-diffusing optical path, thus further modifying both electrochromic mirrors and electrochromic glazing by proper placement of electrodes. Can be easily used as a charge conducting medium (described below). Also, since all the components of the layers are harmless, these layers can be used for windows and mirrors without fear of fluid leakage or the risk of exposure to health or the environment. .

  The thickness of the electrolytic layer can be about 50 μm. Alternatively, the electrolytic layer can be up to about 500 μm thick. In a preferred embodiment, the electrolytic layer thickness is about 120 μm. Since the electrolytic layer 16 is extremely thin, thinner electrochromic assemblies (thin profiles) can be produced compared to conventional structures.

  Referring now to FIG. 3 a, the membrane 10 comprises electrochrome in the form of an electrochromic layer 18 that is in contact with at least a portion of the surface 13 of the membrane 10. In this embodiment, the first electrochromic layer 18 is in contact with at least a portion of the first surface (surface 13b) of the membrane 10, and the second electrochromic layer 20 is on the opposite surface. That is, it is in contact with at least a part of the second surface (surface 13a) of the membrane 10. However, it will be appreciated that in some systems, either electrochromic layer is sufficient to contact the membrane 10. FIG. 3b shows that type of structure. Further, a plurality of electrochromic layers may be present on the first or second surface of the membrane as required (not shown).

  The electrochromic material forming the electrochromic layers 18 and 20 is colored according to the frequency of light absorbed by the electrochrome. The electrochromes forming the electrochromic layers 18 and 20 are complementary to each other such that the electrochromic layer 18 is anodically colored while the electrochromic layer 20 is cathodically colored. Selected to have an absorption spectrum.

  In this embodiment, the electrochromic layers 18 and 20 are essentially conductive polymers selected from the group of polythiophene, polypyrrole, polyaniline, polyindole, polycarbazole, polyphenylene sulfide and polyparaphenylene and derivatives thereof. (ICP; inherently conducting polymers). Optionally, a compound selected from these groups can be substituted with at least one chemical functional group. Alternatively, the intrinsically conductive polymer is a copolymer, block copolymer or graft that can each contain one or more different monomers or oligomers selected from the above group. It is also possible to contain a copolymer. For example, it may contain a series of thiophene units followed by a series of indole units or pyrrole units.

  In addition, the intrinsically conductive polymer may contain, in whole or in part, various other polymers not listed above and / or a composite. It is also possible to use in addition to the monomer unit or the oligomer unit. In some cases, an intrinsically conductive polymer may be essentially unprocessable, and thus a composite such as polystyrene sulfonic acid (PSS) may be used to impart different properties to the polymer. The processability can be improved.

  In this example, the electrochromic layer 18 is cathodically colored and is formed from polyethylenedioxy-thiophene (PEDOT) doped with polystyrene sulfonic acid (PSS). PEDOT has a low redox potential, is stable against multiple redox switching, and has a high conductivity. These characteristics are due to the high electron density of the molecular structure. Another cathodic colored electrochrome that can be used is polypropylene dioxythiophene (PRODOT). The electrochromic layer 20 is anodic colored and is made of polypyrrole (PPy). Other anodic coloring electrochromes that can be used include, for example, polyaniline. As mentioned above, there are several other ICPs (ICPs) that can be used, in fact, using other types of electrochrome, such as conjugated polymers or metal oxides, on the surface of the membrane 10. You will understand that you can.

  Electrochromic layers 18 and 20 are coated on surfaces 13a and 13b using known printing methods such as ink jet, roll / press printing, silk screening or air brushing. One skilled in the art will appreciate that any method for contacting the electrochrome 18 and 20 to the membrane can be used, such as solution casting, dip coating or spin coating. Alternatively, the electrochromic layer can be deposited by vacuum filtration. The electrochromic layer can be formed on top of the membrane 10, or alternatively, the membrane 10 can be filled with an electrochromic layer. FIG. 2b is a close-up view of membrane 10 having an electrochromic layer thereon.

  Optionally, performance additives are added to the essentially conductive polymer (or other part of the assembly) to improve the electrochromic layer deposition process. For example, wetting agents such as nonionic surfactants can be used to reduce the surface tension of the solution to which ICPs are deposited, thereby improving the adhesion of the electrochromic layer to the target material. Other performance additives can also be used advantageously to improve the adhesion, UV stability, harmony (consistency), lifetime, flexibility or adhesion of the electrochromic layer, preservative additives , Rheological additives and / or antifoaming agents.

  Optionally, a conductive additive is added to either or both ICP layers to improve the conductivity of the ICP. Conductive additives that can be used in the present invention include indium tin oxide (ITO) microparticles. It should be understood that other known additives for improving the conductivity (and hence performance) of the electrochromic layer can also be used. If the conductive additive is sufficiently conductive, the electrochromic layer and the electrode layer are the same layer. Since the conductive electrochromic layer performs both a conductive function and an electrochromic function, it is not necessary to deposit an electrochromic layer and a separate electrode layer.

  FIG. 4 a shows an electrolytic layer 16 and electrochromic layers 18, 20 disposed between two electrodes, one electrode 22 and the other counter electrode 24. The PVDF membrane of the electrolytic layer (i.e., charge conducting medium) 16 is pre-formed and thus serves to evenly separate the electrode 22 and the counter electrode 24 from each other. The formed electrochromic assembly has essentially continuous spacers, which is easier to manufacture because the electrode separation is essentially predetermined (defined) It means that. The resulting assembly also has better resistance to knock strain, gravity strain, temperature strain and pressure strain.

  Electrodes 22 and 24 are indium tin oxide (ITO), but any suitable electrode that is substantially transparent, such as fluorine-doped tin oxide (FTO), antimony-doped tin oxide or other conductive metal oxide or metal thin film Can be used. In a preferred embodiment, an ITO electrode is deposited on the top membrane 10 of the electrochromic layers 18 and 20.

  Also, optionally, an electrode is deposited on the membrane 10 prior to deposition of the electrochromic layers 18 and 20 (FIG. 4b). When placing an electrode between the membrane 10 and the electrochromic layers 18 and 20, the electrode is porous, transparent and flexible, and does not limit the inherent porosity of the membrane 10 without limiting the membrane's inherent porosity. Can be easily attached. (If electrodes are deposited on top of the electrochromic layers 18 and 20, they need not be made porous). Alternatively, one electrode can be sandwiched as shown in FIG. 4a and the other electrode can be placed on top of the electrochromic layer as shown in FIG. 4b. FIG. 4c shows this structure. In the structure described above, all the electrodes are always in contact with the electrochromic layer, and in effect the electrochromic layer covers at least part of the electrode.

  When used in a dimming mirror, the assembly must further include a reflective surface. The electrochromic assembly can be in contact with the reflective surface, or the reflective surface can be formed as an integral part of the electrochromic assembly (ie, the reflective surface can be an electrode).

  The membrane on which the electrochromic layers 18, 20 and / or electrodes 22, 24 are deposited (the membrane shown in FIGS. 4a-4c, described above) is a flexible subassembly. “Flexible” means that the assembly has a flexibility of 400 mm in diameter, more preferably flexibility of 100 mm in diameter. By imparting this flexibility, the membrane 10 with the electrochromic layers 18, 20 and / or electrodes 22, 24 deposited thereon can optionally be stored prior to use. . For example, the membrane 10 can be formed on a spool as an elongated laminated sheet, which can be wound up and stored. Conveniently, a portion of the wound membrane 10 can be removed from the roll or cut as required. Next, a portion of the membrane 10 removed or cut from the roll can be combined to make an electrochromic assembly (described below). This type of storage, with easy access to the membrane, is easy in terms of roll delivery and requires no substantial modification prior to use, so from a manufacturing standpoint, in terms of cost and time. This is a significant advantage. Preferably, the ionic liquid 14 is added when the subassembly is ready for use.

  Alternatively, the electrodes can be deposited on a suitable support, such as the first sheet 26 and the second sheet 28, which can be formed from plastic (PET) or glass or the like (FIG. 5a). ). Next, the support can be pressed (pressed) onto a membrane having an electrochromic layer thereon and filled with an ionic liquid (FIG. 5b). At least one of the supports preferably has a reflective surface 30. The reflective surface 30 optionally functions as an electrode, eg, a counter electrode 24. The arrows indicate the incident light that is reflected by the assembly.

  FIG. 5c shows the outer reflective surface 30 of the assembly according to another embodiment of the present invention. In addition, sealing of a membrane using a sealant 42 (epoxy resin or the like) is shown. In addition, a bus 48 is shown that allows the assembly to have a potential applied to the electrodes.

  In yet another alternative, the electrodes 22, 24 and the electrochromic layer can be deposited on a suitable support (or sheet) such as plastic or glass. It is understood that the electrode and the electrochromic layer can be deposited in any order, for example, the electrode can be deposited first and then the electrochromic layer on top (or vice versa). Wanna (not shown). The support can then be pressed (pressed) against the electrolyte layer to form the sandwich or layered structure shown in FIG. 5b. The electrolytic layer can be sealed between the support. In that case, as described above, in some cases, in order to improve (enhance) the electrical contact between the ICP and the electrode, a conductive layer such as a particle, for example, a microparticle, is interposed between the ICP and the electrode layer. It is advantageous to add.

  The material from which the electrochromic assembly is formed is harmless to health or the environment. In the case of the structure according to the invention, the distance between the electrodes is uniformly maintained by means of an electrolytic layer and / or an electrochromic layer arranged between the electrodes. In the structure of the present invention, the spacing between the electrodes cannot change substantially, so the external and internal stresses of this structure do not substantially affect the uniformity of the electric field of the assembly. You won't be bothered by the same problems faced by LCD displays. The assembly can take advantage of the support properties of the pre-formed membrane and support it internally to prevent strain and loss of function due to physical stress.

  The resulting layered structure with the electrolytic layer 16 having electrochromic layers 18 and 20 disposed thereon between the electrodes 22 and 24 constitutes the electrochromic assembly 32. The electrochromic assembly 32 is optically transparent, and a light transmission path is formed between the electrode and the reflective surface. The arrows in FIG. 5 indicate that incident light incident on the electrochromic assembly passes through the electrochromic layers 18, 20, the electrode 22 and the counter electrode 24, passes through the electrolytic layer 16, and is reflected by the reflective surface 30. Show. (In FIG. 5, it is assumed that the electrochromic layer does not substantially interfere with the optical path.) The electrochromic assembly 32 is a self-contained, self-supporting, multi-liquid. assembly) and can be formed in any shape suitable for use.

  By applying a potential between the electrode 22 and the counter electrode 24, a current flows between the electrodes. Charge carriers (ie, ions or electrons) move from either electrochromic layer 18 or 20 to the other (18 or 20), and the absorption spectrum is affected by electrochromic oxidation or reduction, thus 2 Two electrochrome colors are affected.

  The first electrochromic layer and the second electrochromic layer are combined (combined) that are maximal over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. Selected to have an absorption spectrum (as described above). When a reverse potential is applied between the first electrochromic layer and the second electrochromic layer, these layers have an overall (combined) absorption spectrum that is minimal over the visible spectrum. The electrolytic layer 16 is substantially transparent so that the user can see this color change.

  Ideally, the anodic colored electrochromic layer 20 is reduced and transparent to the main part of the visible spectrum. Oxidation induces absorption in the visible region and thereby becomes at least partially colored. In this case, the complementary cathode-colored electrochromic layer 18 is selected to be transparent and very lightly colored when oxidized. When the oxidized form is reduced, the cathode-colored electrochromic layer 18 returns to the colored state.

  Application of a potential to the electrochromic assembly provides a dimming state to the electrochromic assembly. The light transmittance varies depending on the voltage applied between the electrodes. The electrochromic assembly has a good open circuit memory so that certain electrochromic states remain substantially constant for a period of time even when the external voltage potential is removed.

  Also, for safety, means are provided for returning the electrochromic assembly to a non-dimming state in the event of an electrical failure. This means may be an electrical switch that applies the voltage potential required between the electrodes to provide a non-dimming condition. This safety feature is particularly useful for vehicle mirror systems where the vehicle mirror is preferably in a non-dimming state by default.

  By doubling the electrochromic structure, the device can be switched between a highly transmissive state and a highly absorptive state as a function of the applied voltage potential. Also, due to the dual nature of the system, the potential applied to change the color of the electrochromic assembly 32 can be lowered (can be as low as about 1 volt). Since the applied voltage potential is reduced, the life of the assembly 32 is increased.

  It is known that both cations and anions of the ionic liquid 14 enter the electrochromic layers 18 and 20. The ionic liquid 14 facilitates electrochromic oxidation and reduction of the electrochromic layers 18 and 20. For example, when electrochrome is oxidized, cations are discharged together with the remaining anions, and the charges are balanced.

  In conventional structures, counterion movement through the electrochromic assembly is responsible for many problems, including cracking and delamination due to disturbing ion flow and slow response times. Since the flexible electrolytic layer 16 is used in combination with the electrochromic layers 18 and 20 in the structure according to the invention, a system is provided that does not crack or delaminate. Electrochromic layers 18 and 20 are porous and the counterion or charge carrier has a high degree of mobility due to the electrochromic open polymer structure.

  The structure of the membrane 10 further provides elasticity to the entire structure because it does not interfere with the flow of charge carriers. The flexibility and internal structure of the structure according to the present invention further provides an uninhibited ion flow, ie, a charge carrier flow in the electrochromic assembly 32 that is faster than the charge carrier flow found in conventional structures. “Uninhibited flow” means that ions freely flow through the membrane and thus have a relatively fast response time to changes in permeability when an applied potential is applied, often the standard It means that there is no problem of slow response time due to the solid electrolyte system.

  The presence of the membrane 10 actually increases the conductivity of the electrolyte. This is due to the fact that the ionic liquid does not conduct electricity through the direct movement of ions. Instead, the conductive process is caused by small displacements of ions that form “holes” with a net charge. When the counter ion moves into the hole and the charge equilibrates, the counter ion forms another hole (from the position before the counter ion), and this hole equilibrates with another counter ion. In this way, the process continues. In the presence of a material with a large surface area, such as PVDF, a higher energy region is formed or a high energy region is maintained, thus increasing the probability that holes will be formed, and thus the charge transport properties of the system. Is thought to be improved (enhanced).

Table 1 below shows the bulk solution resistance R _s of the ionic liquid in ohms / cm ² . CPE and Rp are parameters derived from the interaction of the ionic liquid and the test cell. The system was modeled using an equivalent circuit with solution resistance Rs in series with Rp (interface resistance) and CPE (Constant Phase Element) connected in parallel.
Table 1 shows the resistance and capacity of the ionic liquid used without the membrane.

Table 2 below shows the resistance R _s in ohm / cm ² of the electrolytic layer or charge conducting medium (ie PVDF membrane filled with ionic liquid).
Table 2 shows the resistance and capacity of the ionic liquid filled in the membrane.

It is clear that the resistance R _s is smaller when the membrane is filled with ionic liquid (compared to R _s measured with ionic liquid only). Therefore, the membrane effectively increases the conductivity of the ionic liquid and does not suppress the movement of ions.

FIG. 8 shows an overview of the variables measured in Tables 1 and 2. 9a and 9b are Bode plots using the variables of Table 1, and FIGS. 10a and 10b are Bode plots of the variables using the variables of Table 2.
The membrane is pre-formed (ie, the membrane is provided without the electrochromic and / or electrode layers and with the ionic liquid not being filled). The size of the membrane pores is selected so that the unsuppressed charge carriers and ions flow in both directions and are not disturbed or suppressed by any charge within the membrane 10 itself. The response time of the system to a change from a dimming state to a non-dimming state (that is, a change from transparent to non-transmissive) is about several seconds (about 1 second).

FIG. 7 shows the change in transmittance (intensity of transmitted light) of the assembly over a number of cycles in arbitrary units (au). One cycle consists of applying a potential and applying a reverse potential. In either case, these response times (shown in the graph of FIG. 7) relate to the time required to dim to 90% of the final dark state or the time required to brighten to 90% of the final bright state. Is about 1 second.
This response time is at least an order of magnitude faster than prior art structures. Furthermore, the structure according to the invention has a lifetime that is at least an order of magnitude longer than the structure according to the prior art.

  By selecting an intermediate potential, the color of electrochrome can be changed from a dim color, a light color, and a variable shade in between. Therefore, the structure according to the present invention is easy to control and can be dimmed in correlation with the intensity of incident light.

  Although the present invention has been described as a layered mold structure forming a sheet or membrane, it is also possible to provide the assembly as an electrochromic wire or electrochromic fiber. FIG. 6 illustrates another embodiment of the present invention in which PVDF is disposed between the electrochromic layers 18 and 20 and between the electrodes 22 and 24 in an annular structure. According to this structure, an electrochromic wire or an electrochromic fiber that can have any desired length can be obtained. When an ionic liquid is added to the wire or fiber, the resulting electrochromic assembly functions substantially the same as the sheet-type structure described herein. Those skilled in the art will appreciate that other configurations that function in a manner similar to the structures described herein are also contemplated as within the scope of the present invention.

  The present invention also provides a method of manufacturing an electrochromic subassembly and / or assembly. A method for preparing a subassembly includes providing a pre-formed porous flexible membrane, adding a first conductive material to a first side of the membrane, and a second side of the membrane. And adding a second conductive material. The conductive material is ITO described above. The method also includes the steps of adding a first electrochromic material to the first side of the membrane and adding a second electrochromic material to the second side of the membrane. The conductive material and the electrochromic material can be added in any order.

  When these layers are added, the membrane is filled with electrolyte, thereby forming a substantially transparent assembly having a light transmission that varies with the voltage applied between the electrodes (described above). As you did).

  Optionally, an electrochromic layer and an electrode layer are deposited on the first and second transparent sheets or supports. (As explained above, the electrochromic layer can optionally be made sufficiently conductive by adding a conductive additive, and a separate electrode layer can be dispensed with). The prepared support can sandwich the porous flexible membrane 10 in a sandwich, the porous flexible membrane can be substantially transparent, and as described above. It can be made charge conductive by filling the membrane with an ionic liquid having a compatible refractive index. Once formed, the assembly membrane and electrolyte are sealed between the supports, for example using an epoxy resin, before applying a potential across the assembly to change the light transmission. It is preferable. It is also possible to use other suitable sealants, for example polyurethane adhesives.

  The structure according to the invention is used in an electrochromic mirror for changing the intensity of reflected light incident on the mirror. A mirror capable of reversibly dimming can be used in the automotive industry. The structure according to the invention can also be used for electrochromic glazing, where changes in the color or transmittance of the assembly can provide dimming conditions for windows or other types of screens. This dimming can improve the level of privacy in a certain area and can control the level of radiant heat transmitted to a certain area. Electrochromic glazing can be used in many industries including the automotive industry, the building industry and the aviation industry.

  Also, the electrochromic assembly according to the present invention can optionally have applications in visual displays, for example in projector light modulators that can improve upon current LCD projector technology. A visual display incorporating the present invention can be used for advertising. By manipulating the electric field, advertisements can be displayed on the electronic billboard. Advertisements can be easily replaced by providing the ability to display multiple advertisements on one billboard by changing the potential. Furthermore, dimming of electrochromic assemblies can be used advantageously in the eye related industry. To correct the amount of light sent to the eye, the tint and color of the lens can be adjusted manually or automatically.

  Any industry that benefits from color and / or reflectance changes in the visible spectrum can utilize this technology. Color adjustment can have applications in the fashion industry in some cases, and flexible laminates or mesh fibers with a system according to the present invention can provide many different colors for textiles, jewelry and cosmetics. Also, the color of the wallpaper can be changed by optionally using a color change in the room fixture, for example by applying an applied potential.

  Various means can be provided to control the potential applied to the electrochromic assembly 32, thereby providing various dimming and non-dimming states. This is particularly advantageous for vehicle rear view mirrors that require activation when glare occurs in the mirrors due to headlights. For example, a photoelectric switching device in the form of a photovoltaic cell such as a photodiode, phototransistor or LDR can be used as the input of the control means. When the vehicle headlight followed by the photoelectric switch is perceived, the control means can be activated to provide a potential across the electrodes. It is also possible to provide, for example, a self-powered dimmable mirror using a photovoltaic cell and a power storage device such as a battery. Various other components and control means can also be used.

Example 1
In one embodiment of the present invention, a glass support (size 30 cm × 30 cm) with a thin ITO film acting as an electrode and a metal strip (indium solder) constructing the first electrode along one edge On top of poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate), Aldrich Cat no. 483095 (PEDOT) was airbrushed.
Polypyrrole (PPY) was airbrushed onto a second glass support (size 30 cm × 30 cm) with another ITO metal strip (ITO) with an ITO electrode passing along one edge. The loading of the conductive polymer onto the electrodes was determined by measuring the transmittance of the individual electrodes with a spectrophotometer (Hunterlab Colorquest XE). In the case of PEDOT, the optimal loading corresponded to 55% photopic transmission, and in the case of PPY, the optimal loading corresponded to 60% photopic transmission. This was determined by horizontal electron microscopy to be equal to a film thickness of about 100 nm.

The electrodes were collected and combined around a PVDF (polyvinylidene difluoride) membrane filled with an ionic liquid (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide).
The assembly was sealed with a two part epoxy resin. A potential of 1.5 V was applied to the metal strip (bus bar). It became substantially uniformly dim, and when the potential was reversed, it became substantially uniformly bright.

  FIG. 7 shows the change in the transmittance (intensity of transmitted light) of a cell over a large number of cycles in arbitrary units (au) (one cycle is a potential application and a reverse potential application). Is made up of). An assembly can be characterized by its response time: either in terms of the time required to dim to 90% of the final dark state or the time required to brighten to 90% of the final bright state These response times (shown in the graph of FIG. 7) are about 1 second.

  Also, when the potential is removed, the cell returns to the intermediate state very slowly (about 3 hours). This memory (temporary storage) is advantageous because it means that the assembly consumes little power to maintain its desired state.

Example 2
In another embodiment of the present invention, PRODOT (polypropylene dioxy) on a glass support (size 10 cm × 10 cm) comprising an ITO electrode and a metal strip constructing the first electrode along one edge. Thiophene) was attached. Polyaniline was airbrushed onto the second glass support.
The electrodes were collected and combined around a PVDF (polyvinylidene difluoride) membrane filled with an ionic liquid (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide).
The assembly was sealed with a two-part epoxy resin. A potential of 1.5 V was applied to the metal strip (bus bar). It became substantially uniformly dim, and when the potential was reversed, it became substantially uniformly bright. The response time for each transition was about 1 second.

Example 3
In another embodiment of the present invention, PEDOT (polyethylenedioxythiophene) is airbrushed on a polyethylene terephthalate support (size 7 cm × 7 cm) with an ITO electrode and a metal strip running along one edge. It was done. PPY (polypyrrole) was airbrushed onto a second support (size 7 cm × 7 cm) also provided with metal strips.
The electrodes were collected and combined around a PVDF (polyvinylidene difluoride) membrane filled with an ionic liquid (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide).
The assembly was sealed with polyurethane adhesive and a 1.5 V potential was applied to the metal strip (bus bar). It became faint uniformly and became brighter when the potential was reversed. The assembly was bent at about 100 mm in diameter and continued to operate.

Example 4
In another embodiment of the invention, a substantially transparent conductive ITO electrode was sputtered on both sides of the PVDF membrane. The two electrodes were electrically separated from each other by the membrane. Conductive epoxy resin was added to both sides of the PVDF membrane to form a bus bar along one edge. A wire was bonded to each of the busbars via a conductive epoxy resin.
The PEDOT layer was airbrushed on one side (first side) of the membrane and the PPY layer was airbrushed on the other side (second side) of the membrane. By this method, intimate contact between the conductive polymer and the electrode could be achieved.
The membrane was filled with an ionic liquid (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide) to form an electrolytic layer (ie, a charge conducting medium). The assembly was then supported between two glass plates and sealed using a two-part epoxy resin.
When an electrical potential was applied, the assembly became substantially dim, and when the electrical potential was reversed, the assembly became substantially bright.

  While the present invention has been described in connection with preferred embodiments to facilitate a better understanding of the invention, it will be understood that various modifications can be made without departing from the principles of the invention. I want to be. Accordingly, it is to be understood that the invention includes all such modifications within its scope.

FIG. 1a is a schematic cross-sectional view of a membrane according to a preferred embodiment of the present invention. FIG. 1b is a schematic cross-sectional view of an electrolytic layer according to a preferred embodiment of the present invention. FIG. 2a is a close-up view of the membrane shown in FIG. 1a. FIG. 2b is a close-up view of the membrane shown in FIG. 1a with an electrochromic layer. FIG. 3a is a schematic cross-sectional view of the electrolytic layer shown in FIG. 1b having an electrochromic layer thereon. FIG. 3b is a schematic cross-sectional view of an electrolytic layer having one electrochromic layer thereon according to another embodiment of the present invention. FIG. 4a is a schematic cross-sectional view of an electrochromic assembly according to a preferred embodiment of the present invention. FIG. 4b is a schematic cross-sectional view of an electrochromic assembly according to another embodiment of the present invention. FIG. 4c is a schematic cross-sectional view of an electrochromic assembly according to another embodiment of the present invention. FIG. 5a is a schematic cross-sectional view of the electrochromic assembly prior to assembly. FIG. 5b is a schematic cross-sectional view of the electrochromic assembly shown in FIG. 5a after assembly. FIG. 5c is a schematic cross-sectional view of an electrochromic assembly according to another embodiment of the present invention. 6 is a schematic cross-sectional view of an electrochromic assembly according to another embodiment of the present invention. FIG. Figure 6 is a graph showing the change in transmittance over multiple cycles of an electrochromic assembly. Fig. 4 is a schematic diagram showing impedance measurements performed on a membrane (both when the pores are filled with ionic liquid and when they are not filled). FIG. 9a is a Bode plot of measurements performed on an ionic liquid (ie, without a membrane). FIG. 9b is a Bode plot of the measurements performed on the ionic liquid (ie without membrane). FIG. 10a is a Bode plot of measurements performed on a membrane filled with ionic liquid. FIG. 10b is a Bode plot of measurements performed on a membrane filled with ionic liquid.

Claims (94)

First and second flexible electrodes, at least one of which is transparent;
A porous flexible membrane having a plurality of pores, the porous flexible membrane having a first refractive index and disposed between the electrodes; and At least one electrochromic layer covering at least a portion of either one or the second electrode;
An electrochromic subassembly comprising:
The subassembly is flexible and transmits an electrolyte having a second refractive index that is substantially matched to the first refractive index, and the electrolyte and subassembly together are substantially transparent. The electrochromic subassembly, which can form a simple electrochromic assembly.   The electrochromic subassembly of claim 1, wherein the subassembly has a flexibility of 400 millimeters in diameter.   The electrochromic subassembly of claim 2, wherein the subassembly has a flexibility of 100 millimeters in diameter.   The electrochromic sub of claim 1, wherein the electrolyte is selected from the group comprising an ionic liquid, an essentially non-liquid salt, a solvent, a polymer having an anionic functional group or a cationic functional group. assembly.   The electrochromic subassembly of claim 4, wherein the electrolyte is an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.   The electrochromic sub of claim 2, wherein the assembly comprises a first electrochromic layer on a first side of the membrane and a second electrochromic layer on a second side of the membrane. assembly.   The electrochromic subassembly of claim 6, wherein the first electrochromic layer has an absorption spectrum that is complementary to an absorption spectrum of the second electrochromic layer.   The total absorption of the first electrochromic layer and the second electrochromic layer that is maximum over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. The electrochromic subassembly of claim 6 having a spectrum.   The first electrochromic layer and the second electrochromic layer are the smallest over the visible spectrum when a reverse potential is applied between the first electrochromic layer and the second electrochromic layer. 9. The electrochromic subassembly according to claim 8, having an absorption spectrum.   The electrochromic subassembly of claim 6, wherein the at least one electrochromic layer contains an essentially conductive polymer.   The essentially conductive polymer is polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polycarbazole and derivatives thereof, polyphenylene sulfide and derivatives thereof, polyparaphenylene and derivatives thereof, or polyindole and derivatives thereof. 11. The electrochromic subassembly of claim 10 containing one or more monomer units or oligomers selected from the group comprising:   The electrochromic subassembly of claim 10, wherein the first electrochromic layer contains poly-3,4-alkylenedioxy-thiophene.   The electrochromic subassembly of claim 12, wherein the second electrochromic layer is polypyrrole.   The electrochromic subassembly of claim 2, wherein the at least one electrochromic layer further comprises a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives, and antifoam agents.   The electrochromic subassembly of claim 2, wherein the at least one electrochromic layer further contains a conductive additive that substantially improves the conductivity of the electrochromic layer.   The electrochromic subassembly of claim 15, wherein the conductive additive contains particles of indium tin oxide (ITO).   The electrochromic subassembly according to claim 2, wherein the electrode is selected from the group comprising indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO).   The electro of claim 17, wherein at least one of the electrodes has a plurality of pores, the pores of the electrode being capable of transporting ions through the electrodes by them. Chromic subassembly.   The electrochromic subassembly of claim 2, wherein the porous flexible membrane comprises a polymer.   20. The electrochromic subassembly of claim 19, wherein the porous flexible membrane contains polyvinylidene difluoride (PVDF).   20. The electrochromic subassembly of claim 19, wherein the membrane is substantially opaque in the visible spectrum.   The electrochromic subassembly of claim 2, wherein the pores of the flexible membrane have tortuous passages through the membrane that allow the electrolyte to pass through the membrane.   23. The electrochromic subassembly of claim 22, wherein the pore size of the porous membrane is between 50 nm and 100 [mu] m.   24. The electrochromic subassembly of claim 23, wherein the pore size of the porous membrane is between 0.1 [mu] m and 5 [mu] m. First and second electrodes, at least one of which is transparent;
A porous membrane having a plurality of pores, the porous membrane having a first refractive index and disposed between the electrodes;
An electrolyte filling the pores, wherein the electrolyte has a second refractive index that substantially matches the first refractive index, and the electrolyte and membrane together are substantially transparent Forming an electrolyte layer; and at least one electrochromic layer covering at least a portion of either the first or second electrode;
Electrochromic assembly with   26. The electrochromic assembly of claim 25, wherein the membrane is flexible and the spacing between the first electrode and the second electrode is maintained substantially constant by the membrane.   26. The electrochromic assembly of claim 25, wherein the assembly is flexible.   26. The electrochromic assembly of claim 25, wherein the electrolyte is selected from the group comprising a polymer having an ionic liquid, an essentially non-liquid salt, a solvent, an anionic functional group or a cationic functional group. .   30. The electrochromic assembly of claim 28, wherein the electrolyte is an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.   26. The electrochromic assembly of claim 25, wherein the assembly comprises a first electrochromic layer on the first side of the membrane and a second electrochromic layer on the second side of the membrane. .   31. The electrochromic assembly of claim 30, wherein the first electrochromic layer has an absorption spectrum that is complementary to the absorption spectrum of the second electrochromic layer.   The total absorption of the first electrochromic layer and the second electrochromic layer is maximum over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. 32. The electrochromic assembly of claim 30, having a spectrum.   The first electrochromic layer and the second electrochromic layer are the smallest over the visible spectrum when a reverse potential is applied between the first electrochromic layer and the second electrochromic layer. 35. The electrochromic subassembly of claim 32, having an absorption spectrum.   32. The electrochromic assembly of claim 30, wherein the at least one electrochromic layer contains an essentially conductive polymer.   The essentially conductive polymer is polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polycarbazole and derivatives thereof, polyphenylene sulfide and derivatives thereof, polyparaphenylene and derivatives thereof, or polyindole and derivatives thereof. 35. The electrochromic assembly of claim 34 containing one or more monomer units or oligomers selected from the group comprising:   35. The electrochromic assembly of claim 34, wherein the first electrochromic layer contains poly-3,4-alkylenedioxy-thiophene.   40. The electrochromic assembly of claim 36, wherein the second electrochromic layer is polypyrrole.   26. The electrochromic assembly of claim 25, wherein the at least one electrochromic layer further contains a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives, and antifoam agents.   26. The electrochromic assembly of claim 25, wherein the at least one electrochromic layer further contains a conductive additive that substantially improves the conductivity of the electrochromic layer.   40. The electrochromic assembly of claim 39, wherein the conductive additive comprises particles of indium tin oxide (ITO).   26. The electrochromic assembly of claim 25, wherein the electrode is selected from the group comprising indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO).   42. The electro of claim 41, wherein at least one of the electrodes has a plurality of pores, the pores of the electrode being capable of transporting ions through the electrodes thereby. Chromic assembly.   26. The electrochromic assembly of claim 25, wherein the porous flexible membrane contains a polymer.   44. The electrochromic assembly of claim 43, wherein the porous flexible membrane comprises polyvinylidene difluoride (PVDF).   26. The electrochromic assembly of claim 25, wherein the membrane is substantially opaque in the visible spectrum.   26. The electrochromic assembly of claim 25, wherein the pores of the flexible membrane have tortuous passages through the membrane that allow the electrolyte to pass through the membrane.   47. The electrochromic assembly of claim 46, wherein the pore size of the porous membrane is between 50 nm and 100 μm.   48. The electrochromic assembly of claim 47, wherein the pore size of the porous membrane is between 0.1 μm and 5 μm.   49. The electrochromic assembly according to any one of claims 25 to 48, further comprising a reflective surface, wherein the assembly forms an electrically dimmable mirror.   50. The electrochromic assembly of claim 49, wherein the reflective surface is formed by either the first or the second electrode.   51. The assembly of any one of claims 25 to 50, wherein the assembly further comprises means for changing a voltage potential between the electrodes, wherein a change in the potential induces a change in light transmittance of the assembly. Electrochromic assembly as described in 1. A preformed porous membrane having a first refractive index having a plurality of pores;
An ionic liquid filling the pores, wherein the ionic liquid has a second refractive index that substantially matches the first refractive index, and the ionic liquid and the membrane together An ionic liquid forming a substantially transparent layer;
At least one essentially conductive polymer electrochromic layer covering at least a portion of the membrane;
A charge conducting medium comprising:
The pores of the membrane have a size such that substantially uninhibited ions flow through the membrane so that ions of the ionic liquid can interact with the electrochromic layer; Charge conducting medium. A first electrode; and a second electrode spaced from the first electrode, wherein the charge conducting medium and the electrochromic layer are disposed between the electrodes;
53. The charge conducting medium of claim 52, further comprising:   54. The charge conductive medium of claim 53, wherein the charge conductive medium has a flexibility of 400 millimeters in diameter.   55. The charge conducting medium of claim 54, wherein the charge conducting medium has a flexibility of 100 millimeters in diameter.   55. The charge conducting medium of claim 54, wherein the electrolyte is selected from the group comprising an ionic liquid, an essentially non-liquid salt, a solvent, a polymer having an anionic functional group or a cationic functional group.   55. The charge conducting medium of claim 54, wherein the electrolyte is an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.   55. The charge conducting medium of claim 54, wherein the assembly comprises a first electrochromic layer on the first side of the membrane and a second electrochromic layer on the second side of the membrane.   59. The charge conducting medium of claim 58, wherein the first electrochromic layer has an absorption spectrum that is complementary to the absorption spectrum of the second electrochromic layer.   The total absorption of the first electrochromic layer and the second electrochromic layer is maximum over the visible spectrum when a potential is applied between the first electrochromic layer and the second electrochromic layer. 59. The charge conducting medium of claim 58, having a spectrum.   The first electrochromic layer and the second electrochromic layer are the smallest over the visible spectrum when a reverse potential is applied between the first electrochromic layer and the second electrochromic layer. 61. The electrochromic subassembly of claim 60 having an absorption spectrum.   55. The charge conducting medium of claim 54, wherein the at least one electrochromic layer contains an essentially conductive polymer.   The essentially conductive polymer is polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polycarbazole and derivatives thereof, polyphenylene sulfide and derivatives thereof, polyparaphenylene and derivatives thereof, or polyindole and derivatives thereof. 64. The charge conducting medium of claim 62, comprising one or more monomer units or oligomers selected from the group comprising:   64. The charge conducting medium of claim 62, wherein the first electrochromic layer contains poly-3,4-alkylenedioxy-thiophene.   The charge conducting medium of claim 64, wherein the second electrochromic layer is polypyrrole.   55. The charge conducting medium of claim 54, wherein the at least one electrochromic layer further contains a performance additive selected from the group comprising preservative additives, wetting agents, rheology additives and antifoam agents.   55. The charge conducting medium of claim 54, wherein the at least one electrochromic layer further contains a conductive additive that substantially improves the conductivity of the electrochromic layer.   68. The charge conducting medium of claim 67, wherein the conductive additive contains particles of indium tin oxide (ITO).   55. The charge conducting medium of claim 54, wherein the electrode is selected from the group comprising indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO).   70. Charge according to claim 69, characterized in that at least one of the electrodes defines a plurality of pores, the pores of the electrode being capable of transporting ions through the electrodes thereby. Conductive medium.   55. A charge conducting medium according to claim 54, wherein the porous flexible membrane comprises a polymer.   72. The charge conducting medium of claim 71, wherein the porous flexible membrane comprises polyvinylidene difluoride (PVDF).   55. A charge conducting medium according to claim 54, wherein the membrane is substantially opaque in the visible spectrum.   55. The charge conducting medium of claim 54, wherein the pores of the flexible membrane have tortuous passages through the membrane that allow the electrolyte to pass through the membrane.   75. The charge conducting medium of claim 74, wherein the pore size of the porous membrane is between 50 nm and 100 [mu] m.   76. The charge conducting medium of claim 75, wherein the pore size of the porous membrane is between 0.1 and 5 [mu] m. Providing first and second transparent sheets each having a conductive electrochromic layer forming an electrode;
Providing a preformed porous flexible membrane having a first refractive index;
Filling the membrane with an electrolyte having a second refractive index substantially matching the first refractive index;
Sealing the membrane and electrolyte between the first sheet and the second sheet;
Forming a substantially transparent electrochromic assembly having a light transmittance that varies with the voltage applied between the electrodes by the above steps;
An electrochromic assembly manufacturing method comprising:   78. The method of claim 77, wherein the porous flexible membrane contains a polymer.   79. The method of claim 78, wherein the porous flexible membrane contains polyvinylidene difluoride (PVDF).   79. The method of claim 78, wherein the membrane is selected to have a pore size between 50 nm and 100 [mu] m.   81. The method of claim 80, wherein the membrane is selected to have a pore size between 0.1 [mu] m and 5 [mu] m.   78. The method of claim 77, wherein the electrolyte is selected from the group comprising a polymer having an ionic liquid, an essentially non-liquid salt, a solvent, an anionic functional group or a cationic functional group.   83. The method of claim 82, wherein the electrolyte is an ionic liquid containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide.   The method further comprises the step of adding a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives and antifoaming agents to at least one of the plurality of conductive electrochromic layers. 78. The method of claim 77. Providing a preformed porous flexible membrane having a first refractive index having a plurality of pores;
Adding a first conductive material to the first surface of the membrane to form a first electrode;
Adding a second conductive material to the second surface of the membrane to form a second electrode;
Adding a first electrochromic material to the first side of the membrane;
Filling the membrane with an electrolyte having a second refractive index substantially matching the first refractive index;
Forming a substantially transparent electrochromic assembly having a light transmittance that varies with the voltage applied between the electrodes by the above steps;
A method of manufacturing a flexible electrochromic assembly.   86. The method of manufacturing an electrochromic assembly according to claim 85, further comprising adding a second electrochromic material to the second surface of the membrane. Adding the first conductive material and adding the first electrochromic material is a single step forming a first single layer;
86. The method of manufacturing an electrochromic assembly according to claim 85, wherein the first conductive material and the first electrochromic material are the same material or a mixture of materials.   86. The method of claim 85, wherein the formed assembly has a flexibility of 400 millimeters in diameter.   90. The method of claim 88, wherein the assembly formed has a flexibility of 100 millimeters in diameter.   The method further comprises adding a performance additive selected from the group comprising preservative additives, wetting agents, rheological additives and antifoaming agents to at least one of the plurality of conductive electrochromic layers. 90. The method of claim 85.   86. The method of claim 85, wherein the porous flexible membrane contains a polymer.   92. The method of claim 91, wherein the porous flexible membrane comprises polyvinylidene difluoride (PVDF).   92. The method of claim 91, wherein the membrane is selected to have a pore size between 50 nm and 100 [mu] m.   94. The method of claim 93, wherein the membrane is selected to have a pore size between 0.1 [mu] m and 5 [mu] m.

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